JP5906888B2 - Glass frit and crystallized glass - Google Patents
Glass frit and crystallized glass Download PDFInfo
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- JP5906888B2 JP5906888B2 JP2012076670A JP2012076670A JP5906888B2 JP 5906888 B2 JP5906888 B2 JP 5906888B2 JP 2012076670 A JP2012076670 A JP 2012076670A JP 2012076670 A JP2012076670 A JP 2012076670A JP 5906888 B2 JP5906888 B2 JP 5906888B2
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- 239000011521 glass Substances 0.000 title claims description 163
- 239000000203 mixture Substances 0.000 claims description 62
- 239000003566 sealing material Substances 0.000 claims description 52
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 46
- 238000010304 firing Methods 0.000 description 44
- 239000000843 powder Substances 0.000 description 38
- 238000007789 sealing Methods 0.000 description 38
- 238000005452 bending Methods 0.000 description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910052844 willemite Inorganic materials 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Glass Compositions (AREA)
- Fuel Cell (AREA)
Description
本発明は、ＳｉＯ２−Ｂ２Ｏ３−ＭｇＯ−Ａｌ２Ｏ３系のガラス組成物であって、アルカリ成分を含まず、無機部材同士の封着または接合等に好適な封着用無アルカリガラス組成物、およびそれから作製される封着材に関する。 The present invention is an SiO 2 —B 2 O 3 —MgO—Al 2 O 3 -based glass composition that does not contain an alkali component and is suitable for sealing or bonding between inorganic members. The present invention relates to a composition and a sealing material made therefrom.
金属材料やセラミックス材料等からなる複合部材の製造において、ガラス組成物を主成分とする封着材を焼成し、焼成体にしてこれらの材料同士の封着または接合する方法がある。このとき、前記封着材としては、ガラス組成物を粉砕して作製されたガラス粉体（ガラスフリットともいう）や、このガラスフリットから作製されるプレスフリット等が広く使用されている。 In the manufacture of a composite member made of a metal material, a ceramic material, or the like, there is a method in which a sealing material containing a glass composition as a main component is fired to form a fired body, and these materials are sealed or bonded together. At this time, as the sealing material, glass powder (also referred to as glass frit) produced by pulverizing a glass composition, press frit produced from the glass frit, and the like are widely used.
一方で、固体酸化物型燃料電池（solid oxide fuel cells、以下、ＳＯＦＣという）の化学リアクターのシール材に代表されるように、封着部が高温にさらされる場合においては、従来のガラス組成物から作製される封着材を用いると、焼成体が高温で軟化・変形して、十分な封着ができなかった。 On the other hand, when the sealing part is exposed to a high temperature as represented by a chemical reactor sealing material of solid oxide fuel cells (hereinafter referred to as SOFC), a conventional glass composition is used. When the sealing material produced from the above was used, the fired body was softened and deformed at a high temperature, and sufficient sealing could not be performed.
特許文献１には、ＳＯＦＣのシール材として、熱的に安定な焼成体が得られるホウケイ酸塩からなるガラス組成物の使用が提案されている。しかし、ガラス組成物中に含まれるホウ酸は、被封着材を腐食する原因となりやすく、また、７００〜１０００℃の作業温度においては、封着部の流動性と形状維持の課題を十分に解決できていなかった。 Patent Document 1 proposes the use of a glass composition made of borosilicate as a SOFC sealing material to obtain a thermally stable fired body. However, boric acid contained in the glass composition is likely to cause corrosion of the sealing material, and at the working temperature of 700 to 1000 ° C., the problem of maintaining the fluidity and shape of the sealing portion is sufficient. It was not solved.
特許文献２、３には、ガラス成分中にホウ酸を含まず、または少量含んでも焼成体とした際に結晶を析出させることにより、高い熱的安定性を有する焼成体が得られるガラス組成物が提案されている。そして、この提案されたガラス組成物をガラスフリットまたはガラスペーストの形にして、高温にさらされる部分のシール材に使用することが提案されている。
しかし、特許文献２のガラス組成物には、アルカリ金属酸化物が多量に含まれているため、高い作業温度域、例えば前記ＳＯＦＣの作動温度域において、焼成体内でアルカリ金属成分が拡散するため、封着部の流動性については、十分に解決できていなかった。
However, since the glass composition of
また、特許文献３には、ガラス組成物が酸化物基準のモル％で、ＳｉＯ２ ３５〜４１．５％、ＭｇＯ ８〜２５％、ＣａＯ ２７％超３５％以下、ＳｒＯ ０〜２％、ＢａＯ ０〜４％、ＺｎＯ ５〜１５％、Ａｌ２Ｏ３ ４．５〜１０％含有し、かつこれらの成分の含有量が全体の９７％以上であり、ＳｒＯとＢａＯを含有する場合それらの含有量の合計が２％以下である無鉛ガラス組成物が提案されている。このガラス組成物から作製される封着材を用いて封着した場合、封着温度が９００〜１１００℃と高温となり、熱による被封着材の損傷の問題があった。
Patent Document 3 discloses that the glass composition is mol% based on oxide, and SiO 2 35 to 41.5%, MgO 8 to 25%, CaO more than 27% and 35% or less,
特許文献４には、ガラス組成が、酸化物基準の質量％で、ＳｉＯ２ １０〜３０％、Ｂ２Ｏ３ ２０〜３０％、ＣａＯ１０〜４０％、ＭｇＯ １５〜４０％、ＳｒＯ＋ＢａＯ＋ＺｎＯ ０〜１０％、Ａｌ２Ｏ３ ０〜５％、Ｌａ２Ｏ３ ０〜５％、ＲＯ２（ＲはＺｒ、ＴｉまたはＳｎ） ０〜３％を含む無アルカリガラスが提案されている。提案されたガラスは、封着温度を９００±５０℃と低くでき、また焼成すると結晶が析出するため、ホウ酸を含んでいても被封着材の腐食を抑制できていた。
Patent Document 4, the glass composition, in weight percent on the oxide basis, SiO 2 10~30%, B 2 O 3 20~30%, CaO10~40%, 15~40% MgO, SrO + BaO +
しかし、特許文献４に記載のガラス組成物は、ＣａＯを多量に含むため、線膨張係数が低いβ−ＣａＳｉＯ３（α＝６０〜７０×１０−７／℃）などの結晶が局部的に析出しやすい組成系である。これらの結晶は、線膨張係数の高い被封着材の封着において、封着界面のクラック発生の原因となるおそれがある。 However, since the glass composition described in Patent Document 4 contains a large amount of CaO, crystals such as β-CaSiO 3 (α = 60 to 70 × 10 −7 / ° C.) having a low linear expansion coefficient are locally precipitated. It is an easy-to-use composition system. These crystals may cause cracks at the sealing interface in sealing a sealing material having a high linear expansion coefficient.
前記問題に鑑み、本発明は、アルカリ金属を含まず、かつＣａＯの含有量を低く抑えたガラス組成物で、焼成において線膨張係数の低い結晶が析出せず、かつ焼成体が優れた耐熱性を示すガラス組成物の提供を目的とする。 In view of the above problems, the present invention is a glass composition that does not contain an alkali metal and has a low CaO content, crystals with a low coefficient of linear expansion do not precipitate in firing, and the fired body has excellent heat resistance. It aims at providing the glass composition which shows this.
そして、本発明のガラス組成物から作製される封着材を用いて被封着材を封着すれば、封着界面にクラックが発生せず、被封着材を腐食しないガラス組成物の提供を目的とする。 And if a sealing material is sealed using the sealing material produced from the glass composition of this invention, the glass composition which a crack does not generate | occur | produce in a sealing interface and does not corrode a sealing material will be provided. With the goal.
さらに、封着材として、前記ガラス組成物から作製されるガラスフリットと、前記ガラスフリットから作製されるガラスペースト、プレスフリットおよびグリーンシートの提供を目的とする。 Furthermore, it aims at providing the glass frit produced from the said glass composition as a sealing material, the glass paste produced from the said glass frit, a press frit, and a green sheet.
本発明者らは、上記課題を解決すべく検討を重ねた結果、ＳｉＯ２−Ｂ２Ｏ３−ＭｇＯ−Ａｌ２Ｏ３系のガラス組成物について、成分の含有量を調整することで、このガラス組成物のガラス粉体を９００℃未満の焼成により、焼成体中に線膨張係数の高い結晶が析出し、前記焼成体の線膨張係数が９０〜１３５×１０−７／℃となることを見出した。 As a result of repeated studies to solve the above-mentioned problems, the present inventors have adjusted the content of the components of the SiO 2 —B 2 O 3 —MgO—Al 2 O 3 -based glass composition. By firing the glass powder of the glass composition at a temperature of less than 900 ° C., crystals having a high linear expansion coefficient are precipitated in the fired body, and the linear expansion coefficient of the fired body is 90 to 135 × 10 −7 / ° C. I found it.
すなわち、本発明は、実質的にアルカリ金属酸化物を含有せず、酸化物換算の質量％表示で、
ＳｉＯ２ ２〜３０質量％、
Ｂ２Ｏ３ １０〜３０質量％、
ＭｇＯ ５〜３５質量％、
Ａｌ２Ｏ３ ０を超え１０質量％以下、
ＺｎＯ ０〜２５質量％、
ＢａＯ ０〜３０質量％、
Ｌａ２Ｏ３ ６〜４５質量％、
ＭＯ２ ０〜６質量％（ＭはＣｅ、Ｓｎ、ＺｒおよびＴｉからなる群から選ばれる１種以上の元素）を、含有し、ＣａＯを実質的に含有しないことを特徴とするガラス組成物からなるガラスフリットを提供する。
That is, the present invention substantially does not contain an alkali metal oxide, and is expressed in mass% in terms of oxide,
B 2 O 3 10 to 30 wt%,
MgO 5 to 35% by mass,
Exceeding 10% by mass exceeding Al 2 O 3 0,
ZnO 0-25% by mass,
BaO 0-30% by mass,
La 2 O 3 6~45 wt%,
MO 2 Less than six weight% (M is Ce, Sn, 1 or more elements selected from the group consisting of Zr and Ti), and contains, from the glass composition characterized by containing no CaO substantially A glass frit is provided.
また、本発明は前記ガラス組成物から作製される以下の封着材を提供する。
本発明のガラス組成物を粉砕して作製されることを特徴とするガラスフリット。
本発明のガラスフリットを焼成して得られることを特徴とする焼成体。
本発明のガラスフリットと有機ビヒクル等とを混合して作製されることを特徴とするガラスペースト。
本発明のガラスフリットをプレス成形し、ガラスの軟化点以上の温度で、焼成して作製されることを特徴とするプレスフリット。
本発明のガラスフリットと有機ビヒクル等とを混合して透明樹脂フィルム等へ塗布、乾燥することにより作製されることを特徴とするグリーンシート。
Moreover, this invention provides the following sealing materials produced from the said glass composition.
A glass frit produced by pulverizing the glass composition of the present invention.
A fired body obtained by firing the glass frit of the present invention.
A glass paste produced by mixing the glass frit of the present invention with an organic vehicle or the like.
A press frit produced by press-molding the glass frit of the present invention and firing it at a temperature equal to or higher than the softening point of the glass.
A green sheet produced by mixing the glass frit of the present invention and an organic vehicle, etc., applying the mixture to a transparent resin film, and drying.
本発明のガラス組成物によると、前記ガラス組成物を粉砕して作製するガラス粉体が、焼成の際に良好な流動性を示し、また焼成すると線膨張係数の高い結晶が析出した結晶化ガラスとなり、線膨張係数の高い焼成体が得られる。そのため、前記ガラス粉体から作製される封着材は、線膨張係数が高い被封着材の封着に使用でき、また封着部は、６００〜１０００℃の温度域の高温雰囲気化においても変形せず、優れた耐熱性を示す。さらに、ガラス組成物中にアルカリ成分を含まないため、封着時および封着後で６００〜１０００℃の温度域に曝されても被封着材へのアルカリ成分の拡散による劣化が生じない。さらに、Ｂ２Ｏ３およびＣａＯの含有量が適切に調整されているので、被封着材の腐食および封着界面のクラックの発生を抑制できる。 According to the glass composition of the present invention, the glass powder prepared by pulverizing the glass composition exhibits good fluidity during firing, and crystallized glass in which crystals having a high linear expansion coefficient are precipitated upon firing. Thus, a fired body having a high linear expansion coefficient is obtained. Therefore, the sealing material produced from the glass powder can be used for sealing a sealing material having a high linear expansion coefficient, and the sealing portion can be used in a high-temperature atmosphere in a temperature range of 600 to 1000 ° C. It does not deform and exhibits excellent heat resistance. Furthermore, since an alkali component is not contained in the glass composition, deterioration due to diffusion of the alkali component to the sealing material does not occur even when exposed to a temperature range of 600 to 1000 ° C. during and after sealing. Furthermore, since the contents of B 2 O 3 and CaO are appropriately adjusted, corrosion of the sealing material and generation of cracks at the sealing interface can be suppressed.
本発明のガラス組成物が上記特性を有するため、前記ガラス組成物からなるガラスフリット並びに前記ガラスフリットから作製されるガラスペースト、プレスフリットおよびグリーンシートは、ＳＯＦＣのシール材等として好適である。高温での粘性低下のおそれがないため、シール部の絶縁性やシールの耐久性を良好にできる。 Since the glass composition of the present invention has the above properties, the glass frit made of the glass composition and the glass paste, press frit and green sheet produced from the glass frit are suitable as a sealing material for SOFC. Since there is no risk of a decrease in viscosity at high temperatures, the insulation of the seal part and the durability of the seal can be improved.
本発明のガラス組成物は、ガラス原料を調合し、混合し、溶融した後、急冷することにより作製される。溶融温度は、通常１４００〜１５００℃であるが、ガラス組成によって適切に調整される。そして、通常、本発明のガラス組成物を粉砕してガラス粉体とし、そのガラス粉体を焼成し、焼成体として無機材の封着に使用する。前記粉砕には、ボールミルなどを使用できる。 The glass composition of the present invention is prepared by preparing glass materials, mixing, melting, and rapidly cooling. The melting temperature is usually 1400 to 1500 ° C., but is appropriately adjusted depending on the glass composition. And normally, the glass composition of this invention is grind | pulverized to make glass powder, the glass powder is baked, and it uses for sealing of an inorganic material as a baked body. A ball mill or the like can be used for the pulverization.
本発明のガラス組成物は、その粉体を焼成する際に、９００℃未満の焼成温度で前記焼成体内に結晶相が析出することが好ましい。そして、焼成時間は６０〜１２０分が好ましい。また焼成温度は特に限定されないが、熱による被封着材の損傷を防ぐため、低いほど好ましい。そのため、焼成温度は、より好ましくは８７０℃以下であり、さらに好ましくは８５０℃以下である。一方、下限は特に設定されないが、焼成温度が低いと、ガラス粉体の流動性が低く、被封着材との濡れ性が低くなり、封着力が弱くなる。さらに、結晶が生じにくくなり、本発明の機能を損なうおそれがある。そのため、焼成温度は、好ましくは７８０℃以上であり、より好ましくは８００℃以上である。 When the powder of the glass composition of the present invention is fired, it is preferable that a crystal phase is precipitated in the fired body at a firing temperature of less than 900 ° C. The firing time is preferably 60 to 120 minutes. The firing temperature is not particularly limited, but it is preferably as low as possible in order to prevent damage to the sealing material due to heat. Therefore, the firing temperature is more preferably 870 ° C. or less, and further preferably 850 ° C. or less. On the other hand, although the lower limit is not particularly set, when the firing temperature is low, the flowability of the glass powder is low, the wettability with the sealing material is low, and the sealing force is weakened. Furthermore, it becomes difficult to produce crystals, and the function of the present invention may be impaired. Therefore, the firing temperature is preferably 780 ° C. or higher, more preferably 800 ° C. or higher.
焼成温度の昇温過程は特に限定されないが、例えば、焼成温度よりも低い温度に保持し結晶核を発生させ、その後焼成温度まで昇温し、焼成温度に保持して核を成長させ結晶として析出し、結晶化ガラスとすることが好ましい。焼成温度よりも低い温度としては、核生成速度の大きい温度であり、典型的には、ガラスの示差熱分析曲線（以下、ＤＴＡ曲線という）を利用して求められる。 The temperature raising process of the firing temperature is not particularly limited. For example, it is maintained at a temperature lower than the firing temperature to generate crystal nuclei, and then heated to the firing temperature and held at the firing temperature to grow the nuclei and precipitate as crystals. It is preferable to use crystallized glass. The temperature lower than the firing temperature is a temperature at which the nucleation rate is high, and is typically obtained using a differential thermal analysis curve (hereinafter referred to as a DTA curve) of glass.
本発明のガラス組成物から作製されるガラス粉体は、焼成し封着する際において、収縮し、軟化流動しながら被封着材と接触し、冷却されると、被封着材と焼成体とが一体化する。そのため、昇温時には、ガラス粉体は、流動性が高いことが好ましい。流動性が低いと、焼成後に焼成体と被封着物との間に隙間ができ、十分な封着力が得られない。ガラス粉体の流動性は、例えば、フローボタン法により評価できる。フローボタン法は、１．５ｇのガラス粉体をプレス成形して直径１ｃｍであるサンプル（フローボタン）を作製し、サンプルを昇温してその形状変化により評価する。良好な封着力を得るためには、円柱の短部に丸みが生じる程度の流動性が好ましく、円柱形状を保持できない流動性がより好ましい。 When the glass powder produced from the glass composition of the present invention is fired and sealed, the glass powder shrinks, comes into contact with the sealing material while softening and flowing, and when cooled, the sealing material and the fired body. And unite. Therefore, it is preferable that the glass powder has high fluidity when the temperature is increased. When the fluidity is low, a gap is formed between the fired body and the sealed object after firing, and a sufficient sealing force cannot be obtained. The fluidity of the glass powder can be evaluated by, for example, the flow button method. In the flow button method, a sample (flow button) having a diameter of 1 cm is produced by press-molding 1.5 g of glass powder, and the temperature of the sample is raised and the shape change is evaluated. In order to obtain a good sealing force, a fluidity that causes roundness in the short part of the cylinder is preferable, and a fluidity that cannot maintain the cylindrical shape is more preferable.
前記ガラス粉体の平均粒径を５〜５０μｍとすることが好ましい。前記粒径は、粉砕の条件により調整できる。平均粒径が５μｍ未満の場合には、ガラスが結晶化されやすくなり、ガラスの流動性を阻害する要因になり、被封着材の封着において好ましくない。一方、平均粒径が５０μｍ超では、結晶化する速さが遅くなり、被封着材との反応が促進するおそれがあるため、好ましくない。なお、本明細書においては、前記ガラス粉体の平均粒径は、レーザ回折・散乱式粒度分析計を用いて測定した値をいう。 The average particle size of the glass powder is preferably 5 to 50 μm. The said particle size can be adjusted with the conditions of a grinding | pulverization. When the average particle size is less than 5 μm, the glass is likely to be crystallized, which is a factor that hinders the fluidity of the glass, which is not preferable in sealing the sealing material. On the other hand, when the average particle size exceeds 50 μm, the crystallization speed is slow, and the reaction with the sealing material may be accelerated, which is not preferable. In the present specification, the average particle size of the glass powder refers to a value measured using a laser diffraction / scattering particle size analyzer.
本発明のガラス組成物から作製されるガラス粉体を焼成して得られる焼成体（結晶化ガラス）は、５０体積％以上が結晶化していることが好ましく、７０体積％以上が結晶化していることが、高温下における封着部の安定性や形状維持の特性を発揮できるためより好ましい。 The fired body (crystallized glass) obtained by firing the glass powder produced from the glass composition of the present invention preferably has 50% by volume or more crystallized, and 70% by volume or more is crystallized. It is more preferable because the stability and shape maintaining characteristics of the sealing part at high temperatures can be exhibited.
前記焼成体は、５０〜８００℃における平均線膨張係数（α）が、９０〜１３５×１０−７／℃であることが好ましい。そして、１００〜１３０×１０−７／℃がより好ましく、１１０〜１２５×１０−７／℃がさらに好ましい。９０×１０−７／℃未満では、被封着材と接合して使用するときに線膨張係数のマッチングが困難になり、封着の信頼性が低下するおそれがある。 The fired body preferably has an average coefficient of linear expansion (α) at 50 to 800 ° C. of 90 to 135 × 10 −7 / ° C. And 100-130 * 10 < -7 > / degreeC is more preferable, and 110-125 * 10 < -7 > / degreeC is further more preferable. If it is less than 90 × 10 −7 / ° C., it becomes difficult to match the linear expansion coefficients when used while being bonded to the sealing material, and the reliability of sealing may be lowered.
そのため、前記焼成体には、７０×１０−７／℃より線膨張係数の高い結晶が析出することが好ましい。このような高線膨張係数を有する結晶の例としては、ＢａＺｎＳｉＯ４等のＢａＯ−ＺｎＯ−ＳｉＯ２系結晶（α＝約９０〜１１０×１０−７／℃）、フォルステライト（Ｍｇ２ＳｉＯ６）等のＭｇＯ−ＳｉＯ２系結晶（α＝約９０〜１２０×１０−７／℃）、ＢａＭｇＳｉＯ４等のＢａＯ−ＭｇＯ−ＳｉＯ２系結晶、スアナイト（Ｍｇ２Ｂ２Ｏ５）等のＭｇＯ−Ｂ２Ｏ３系結晶、ＬａＢＯ３等のＬａ２Ｏ３−Ｂ２Ｏ３系結晶等が挙げられる。これらのうち、焼成温度における結晶の変態が少なく、焼成後の封着強度を保つ観点から、ＭｇＯ−Ｂ２Ｏ３系結晶またはＬａ２Ｏ３−Ｂ２Ｏ３系結晶の少なくともいずれかが、主として存在することが、より好ましい。 Therefore, it is preferable that crystals having a linear expansion coefficient higher than 70 × 10 −7 / ° C. precipitate on the fired body. Examples of crystals having such a high linear expansion coefficient include BaO—ZnO—SiO 2 based crystals (α = about 90 to 110 × 10 −7 / ° C.) such as BaZnSiO 4 , forsterite (Mg 2 SiO 6 ). MgO—SiO 2 crystal (α = about 90 to 120 × 10 −7 / ° C.), BaO—MgO—SiO 2 crystal such as BaMgSiO 4 , MgO—B such as suanite (Mg 2 B 2 O 5 ) Examples include 2 O 3 based crystals and La 2 O 3 —B 2 O 3 based crystals such as LaBO 3 . Among these, at least one of the MgO—B 2 O 3 -based crystal and the La 2 O 3 —B 2 O 3 -based crystal is preferable from the viewpoint that the transformation of the crystal at the firing temperature is small and the sealing strength after firing is maintained. More preferably, it is mainly present.
一方、線膨張係数が低い結晶の析出は、封着界面にクラックを発生させる原因となるため、析出しないことが好ましい。例えば、ＣａＯ−ＢａＯ系結晶、ＣａＯ−ＳｉＯ２系結晶（α＝６０〜７０×１０−７／℃）、ＺｎＯ−ＳｉＯ２系結晶（α＝３０〜４０×１０−７／℃）または、ＢａＯ−Ａｌ２Ｏ３−ＳｉＯ２系結晶（α＝３０〜４０×１０−７／℃）が挙げられる。ただし、本発明の範囲においては、ＢａＯ−Ａｌ２Ｏ３−ＳｉＯ２結晶はヘキサセルシアンのような線膨張係数の高い相（α＝８０〜９０×１０−７／℃）も析出するため、多少の析出は許容される。 On the other hand, the precipitation of crystals having a low linear expansion coefficient causes cracks at the sealing interface, so it is preferable that they do not precipitate. For example, a CaO—BaO crystal, a CaO—SiO 2 crystal (α = 60 to 70 × 10 −7 / ° C.), a ZnO—SiO 2 crystal (α = 30 to 40 × 10 −7 / ° C.), or a BaO -Al 2 O 3 -SiO 2 based crystal (α = 30~40 × 10 -7 / ℃) and the like. However, in the scope of the present invention, the BaO—Al 2 O 3 —SiO 2 crystal also precipitates a phase having a high linear expansion coefficient such as hexacelsian (α = 80 to 90 × 10 −7 / ° C.), Some precipitation is allowed.
さらに、前記焼成体は、線膨張係数が前記範囲にあるだけでなく、温度変化に対する線膨張係数の伸び率を示す曲線（以下、線膨張曲線という）が、変曲点を有しないことが好ましく、さらに線膨張曲線の屈曲度（単位：１０−７／℃）が小さいことが好ましい。小さくなるにつれて直線に近づく形になる。なお、本明細書においては、前記屈曲度とは、以下のようにして算出した値をいう。 Further, it is preferable that the fired body not only has a linear expansion coefficient in the above-mentioned range, but also has a curve indicating the expansion rate of the linear expansion coefficient with respect to a temperature change (hereinafter referred to as a linear expansion curve) having no inflection point. Furthermore, it is preferable that the degree of bending (unit: 10 −7 / ° C.) of the linear expansion curve is small. It gets closer to a straight line as it gets smaller. In the present specification, the bending degree refers to a value calculated as follows.
図２に示すように、線膨張曲線の中に明確な屈曲が見られる場合、屈曲している点を中心とした前後５０℃の２点における線膨張係数の差を屈曲度とする。一方、図３のように、線膨張曲線の中に明確な屈曲が見られない場合は、線膨張曲線から、３００〜１０００℃において１００℃ごとに、線膨張係数を算出し、隣り合う線膨張係数の差の最大値を屈曲度とする。なお、屈曲度の算出において線膨張係数は、５０℃を基準として算出する。線膨張曲線の屈曲度は、焼成体中の結晶化していないガラス（以下、非晶質ガラスという）の含有量の指標になり、昇降温過程での瞬間的な体積変化の大きさを示す指標となる。すなわち、屈曲度が大きい場合、非晶質ガラス含有量が高いため、焼成体の構造が弱くなり高線膨張係数の被封着材を封着する際に封着界面にクラックが発生しやすくなる。また、昇降温過程での瞬間的な伸びまたは収縮により、焼成体内部または封着界面にクラックが発生しやすくなる。そのため、線膨張曲線において、変曲点が生じず、屈曲度は１３×１０−７／℃以下が好ましく、屈曲度は１０×１０−７／℃以下がより好ましく、５×１０−７／℃以下がさらに好ましい。 As shown in FIG. 2, when a clear bend is observed in the linear expansion curve, the difference in linear expansion coefficient at two points at 50 ° C. before and after the bent point is defined as the degree of bending. On the other hand, as shown in FIG. 3, when no clear bending is observed in the linear expansion curve, the linear expansion coefficient is calculated from the linear expansion curve every 100 ° C. at 300 to 1000 ° C. The maximum value of the coefficient difference is defined as the degree of bending. In calculating the degree of bending, the linear expansion coefficient is calculated with 50 ° C. as a reference. The degree of bending of the linear expansion curve is an index of the content of non-crystallized glass (hereinafter referred to as amorphous glass) in the fired body, and an index indicating the magnitude of instantaneous volume change during the temperature rising and falling process. It becomes. That is, when the degree of bending is large, the amorphous glass content is high, so that the structure of the fired body becomes weak and cracks are likely to occur at the sealing interface when sealing a sealing material having a high linear expansion coefficient. . Also, cracks are likely to occur in the fired body or in the sealing interface due to momentary elongation or contraction during the temperature raising and lowering process. Therefore, an inflection point does not occur in the linear expansion curve, and the bending degree is preferably 13 × 10 −7 / ° C. or less, and the bending degree is more preferably 10 × 10 −7 / ° C. or less, and 5 × 10 −7 / ° C. The following is more preferable.
前記焼成体の屈伏温度は、好ましくは９００℃以上である。９００℃未満で屈伏してしまうと、封着部位の構造を維持できず変形するおそれがあるため、好ましくない。そのため、より好ましくは、９２０℃以上、さらに好ましくは、９４０℃以上である。 The yield temperature of the fired body is preferably 900 ° C. or higher. If it is bent below 900 ° C., the structure of the sealed portion cannot be maintained and may be deformed, which is not preferable. Therefore, More preferably, it is 920 degreeC or more, More preferably, it is 940 degreeC or more.
次に、本発明のガラス組成物の構成成分について、以下に説明する。
ＳｉＯ２は、ガラス組成物のガラス骨格を形成する成分であり、焼成による焼成体中において高線膨張係数を与えるケイ酸塩結晶の主成分であり、必須成分である。ＳｉＯ２の含有量は、２〜３０質量％である。２質量％未満では、ガラス組成物の製造時にガラス化が困難になる。また、ガラス組成物の製造時に結晶が生じ、ガラス粉体の焼成時の流動性が低くなる。３０質量％超では、結晶が析出する速さが遅くなり、結晶の生成割合（以下、結晶化度という）が低下する。また、ガラス転移点が高くなりすぎ、流動性が低下する。そして、含有量の好ましい範囲は、３〜２７質量％であり、より好ましくは、４〜２５質量％である。
Next, the component of the glass composition of this invention is demonstrated below.
SiO 2 is a component that forms the glass skeleton of the glass composition, is a main component of a silicate crystal that gives a high linear expansion coefficient in a fired body by firing, and is an essential component. The content of SiO 2 is 2 to 30% by mass. If it is less than 2% by mass, vitrification becomes difficult during the production of the glass composition. Further, crystals are produced during the production of the glass composition, and the fluidity during the firing of the glass powder is lowered. If it exceeds 30% by mass, the rate at which crystals precipitate is reduced, and the rate of crystal formation (hereinafter referred to as crystallinity) decreases. Further, the glass transition point becomes too high, and the fluidity is lowered. And the preferable range of content is 3-27 mass%, More preferably, it is 4-25 mass%.
Ｂ２Ｏ３は、ガラス組成物のガラス骨格を形成する成分であり、焼成による焼成体中において高線膨張係数を与えるホウ酸塩結晶の主成分であり、必須成分である。Ｂ２Ｏ３の含有量は１０〜３０質量％である。１０質量％未満では、ガラス組成物の製造時に結晶が生じ、焼成時に所望の流動性が得られない。また３０質量％超では、焼成時の結晶化度が低くなり、焼成体の線膨張曲線の屈曲度が大きくなる。また、焼成時において結晶の析出前に被封着材との間で界面反応が進行し、封着の信頼性が低下するおそれがある。含有量の好ましい範囲は、１２〜２７質量％であり、より好ましくは、１４〜２５質量％である。 B 2 O 3 is a component that forms the glass skeleton of the glass composition, is a main component of borate crystals that gives a high linear expansion coefficient in the fired body by firing, and is an essential component. The content of B 2 O 3 is 10 to 30 mass%. If it is less than 10% by mass, crystals are produced during production of the glass composition, and desired fluidity cannot be obtained during firing. On the other hand, if it exceeds 30% by mass, the degree of crystallinity during firing becomes low, and the degree of bending of the linear expansion curve of the fired body becomes large. In addition, an interfacial reaction may proceed with the material to be sealed before crystal deposition during firing, which may reduce the reliability of sealing. The preferable range of the content is 12 to 27% by mass, and more preferably 14 to 25% by mass.
ＭｇＯは、ガラス粉体の焼成時に結晶を析出させやすくする成分であり、必須成分である。ＭｇＯの含有量は、５〜３５質量％である。５質量％未満では、結晶の析出量が少なく、結晶化度が低下する。そのため焼成体の線膨張係数が低くなり、また高温における封着部の耐熱性が低くなる。一方、３５質量％超では、ガラス組成物の製造時においてガラスが不安定になる。また、結晶化開始温度が低くなりすぎ、結晶が析出する速さが著しく速くなるため、より低温で結晶化しやすくなる。これにより、ガラス粉体の焼成時の流動性が低下し、良好な封着性が得られない。含有量の好ましい範囲は、７〜３０質量％、より好ましくは、１０〜２７質量％である。 MgO is a component that facilitates the precipitation of crystals when the glass powder is fired, and is an essential component. The content of MgO is 5 to 35% by mass. If it is less than 5% by mass, the amount of crystals deposited is small and the crystallinity is lowered. Therefore, the linear expansion coefficient of the fired body is lowered, and the heat resistance of the sealing portion at high temperature is lowered. On the other hand, if it exceeds 35 mass%, the glass becomes unstable during the production of the glass composition. In addition, since the crystallization start temperature becomes too low and the speed of crystal precipitation is remarkably increased, it becomes easier to crystallize at a lower temperature. Thereby, the fluidity | liquidity at the time of baking of glass powder falls, and favorable sealing property cannot be obtained. The preferable range of the content is 7 to 30% by mass, and more preferably 10 to 27% by mass.
Ａｌ２Ｏ３は、ガラス組成物と封着材の化学耐久性を高める成分であり、さらに被封着材との封着力を高める成分であり、必須成分である。Ａｌ２Ｏ３の含有量は、０を超え１０質量％以下である。Ａｌ２Ｏ３を実質的に含有しないと、ガラス組成物の製造において、ガラスが不安定になり、ガラス組成物の粉体が焼成時に所望の流動性を示さない。１０質量％を超えると、焼成体中に低線膨張係数または、３００〜４００℃の間に相転移による体積変化を有するＢａＯ−Ａｌ２Ｏ３−ＳｉＯ２系結晶が多量に析出するため、所望の線膨張係数が得られない。含有量の好ましい範囲は、１．５〜９質量％、より好ましくは、２〜８．５質量％である。 Al 2 O 3 is a component that increases the chemical durability of the glass composition and the sealing material, and further increases the sealing power with the sealing material, and is an essential component. The content of Al 2 O 3 is more than 0 and 10% by mass or less. If Al 2 O 3 is not substantially contained, the glass becomes unstable in the production of the glass composition, and the powder of the glass composition does not exhibit the desired fluidity during firing. If it exceeds 10% by mass, a large amount of BaO—Al 2 O 3 —SiO 2 crystal having a low linear expansion coefficient or a volume change due to phase transition between 300 to 400 ° C. is precipitated in the fired body. The linear expansion coefficient cannot be obtained. The preferable range of the content is 1.5 to 9% by mass, and more preferably 2 to 8.5% by mass.
ＺｎＯは、低温でのガラス粉体の流動性を高め、焼成時において結晶を析出しやすくする成分であり、必須成分でない。ＺｎＯの含有量は０〜２５質量％である。２５質量％超では、低線膨張係数のウィレマイトが析出するおそれがあり、焼成体の化学的耐久性、特に耐酸性が低下する。そのため、含有量は１〜２４質量％が好ましく、２〜２３質量％がより好ましい。また、ＺｎＯを含有する場合には、ＢａＯまたはＣａＯを同時に含有することが好ましい。ＢａＯまたはＣａＯを同時に含有することにより、低線膨張係数のウィレマイトの析出を抑制でき、さらには高線膨張係数のＲＯ−ＺｎＯ−ＳｉＯ２（ＲはＢａ、Ｃａ等）系結晶が析出する。 ZnO is a component that enhances the fluidity of the glass powder at a low temperature and facilitates the precipitation of crystals during firing, and is not an essential component. The content of ZnO is 0 to 25% by mass. If it exceeds 25% by mass, there is a possibility that willemite having a low linear expansion coefficient is precipitated, and the chemical durability, particularly acid resistance, of the fired product is lowered. Therefore, the content is preferably 1 to 24% by mass, and more preferably 2 to 23% by mass. Moreover, when containing ZnO, it is preferable to contain BaO or CaO simultaneously. By simultaneously containing BaO or CaO, the precipitation of low linear expansion coefficient willemite can be suppressed, and RO-ZnO-SiO 2 (R is Ba, Ca, etc.) based crystals having a high linear expansion coefficient are further precipitated.
ＣａＯは、焼成時において結晶を析出しやすくする成分であり、必須成分でない。ＣａＯの含有量は、０〜９質量％である。ＣａＯは低線膨張係数の結晶の主成分でもあり、含有量が１０質量％を超えて、前記低線膨張係数の結晶の析出量が多くなると、被封着材との封着界面におけるクラック発生の原因になる。そのため、含有量は１〜８質量％が好ましく、２〜５質量％がさらに好ましい。さらに、ＣａＯの原料としてよく使用されるＣａＣＯ３は、ガラス原料の溶融において炭酸ガスの揮散量が多く、排気ガスの気流に乗って原料粉末が揮散するキャリーオーバーと言われる現象が発生しやすく、成分の揮散に伴う組成ズレ等の品質低下を招くおそれがある。 CaO is a component that facilitates precipitation of crystals during firing, and is not an essential component. The content of CaO is 0 to 9% by mass. CaO is also the main component of crystals with a low linear expansion coefficient. When the content exceeds 10% by mass and the amount of precipitated crystals with a low linear expansion coefficient increases, cracks occur at the sealing interface with the sealing material. Cause. Therefore, the content is preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. Furthermore, CaCO 3 often used as a raw material for CaO has a large volatilization amount of carbon dioxide gas in the melting of the glass raw material, and a phenomenon called carry-over in which the raw material powder volatilizes on the exhaust gas flow easily occurs. There is a risk of causing quality degradation such as compositional deviation accompanying volatilization of components.
ＢａＯは、高線膨張係数を与えるケイ酸塩結晶の構成成分であり、焼成体の線膨張係数の調整に使用される成分であるが、必須成分でない。例えば、線膨張係数を高くする場合には含有量を高く、低くする場合には、含有量を低くするとよい。ＢａＯの含有量は、０〜３０質量％である。３０質量％超では、結晶化度が低くなり、焼成体のクラック発生の原因になる。含有量は、１〜２７質量％が好ましく、５〜２５質量％がより好ましい。 BaO is a constituent component of the silicate crystal that gives a high linear expansion coefficient, and is a component used to adjust the linear expansion coefficient of the fired body, but is not an essential component. For example, when the coefficient of linear expansion is increased, the content is increased, and when it is decreased, the content is decreased. The content of BaO is 0 to 30% by mass. If it exceeds 30% by mass, the degree of crystallinity will be low, causing cracks in the fired product. The content is preferably 1 to 27 mass%, more preferably 5 to 25 mass%.
Ｌａ２Ｏ３は、高線膨張係数を与えるホウ酸塩結晶の構成成分であり、焼成体の線膨張係数の調整に使用される成分であるが、必須成分でない。また、結晶化度を高める成分であり、線膨張曲線において屈曲度を小さくできる。Ｌａ２Ｏ３の含有量は、０〜４５質量％である。４５質量％超では、ガラス組成物の製造時にガラスが不安定になり、焼成時において、ガラス粉体の流動性が低下する。含有量は、６〜４３質量％が好ましく、１０〜４０質量％がより好ましい。 La 2 O 3 is a constituent component of a borate crystal that gives a high linear expansion coefficient, and is a component used to adjust the linear expansion coefficient of the fired body, but is not an essential component. Moreover, it is a component which raises a crystallinity degree and can make a bending degree small in a linear expansion curve. The content of La 2 O 3 is 0 to 45% by mass. If it exceeds 45 mass%, the glass becomes unstable during the production of the glass composition, and the fluidity of the glass powder decreases during firing. The content is preferably 6 to 43% by mass, and more preferably 10 to 40% by mass.
ＭＯ２（ＭはＣｅ、Ｓｎ、ＺｒおよびＴｉからなる群から選ばれる１種以上の元素）は、ガラスの化学耐久性を高め、焼成時の結晶化度を高める成分であるが、必須成分でない。そして、ＭＯ２は、合量（ＣｅＯ２＋ＳｎＯ２＋ＴｉＯ２＋ＺｒＯ２）で６質量％以下が好ましい。６質量％超では、ガラスの溶融性が低下し、製造時にガラスが不安定になる。含有量の上限は、より好ましくは５質量％以下であり、含有しないことがさらに好ましい。
MO 2 (M is one or more elements selected from the group consisting of Ce, Sn, Zr and Ti) is a component that increases the chemical durability of the glass and increases the crystallinity during firing, but is not an essential component. . Then, MO 2 is the total amount 6% by
ＣｅＯ２は、ガラス組成物中において、酸化剤として作用するため、ガラスペースト、プレスフリットまたはグリーンシートとして使用する場合の脱バイ促進剤として働く成分であるが、必須成分でない。含有量は、１質量％以下が好ましい。ＳｎＯ２、ＴｉＯ２およびＺｒＯ２は、焼成時に結晶核として作用するが、溶融ガラスへの溶解度が低い。そのため含有量はそれぞれ６質量％以下が好ましい。ＳｎＯ２は特に溶融ガラスへの溶解度が低いため、１質量％以下がより好ましい。ただし、ＳｎＯ２は、還元しやすい金属酸化物であり、還元性雰囲気化で金属化するおそれがある。 CeO 2 acts as an oxidant in the glass composition, and is therefore a component that acts as a de-buying accelerator when used as a glass paste, press frit, or green sheet, but is not an essential component. The content is preferably 1% by mass or less. SnO 2 , TiO 2, and ZrO 2 act as crystal nuclei during firing, but have low solubility in molten glass. Therefore, the content is preferably 6% by mass or less. Since SnO 2 has a particularly low solubility in molten glass, it is more preferably 1% by mass or less. However, SnO 2 is a metal oxide that is easily reduced, and may be metallized in a reducing atmosphere.
ＭｇＯ＋ＺｎＯ＋Ｌａ２Ｏ３の合量は、４５〜６０モル％が好ましい。焼成時のガラス粉体の流動性、焼成体の結晶化度および焼成体の線膨張曲線の屈曲度に影響する。なかでも他のガラス成分と比べても、屈曲度に特に影響を与える成分であり、本発明においては、図２記載のとおりの相関があることを見出している。すなわち、４５モル％未満では、結晶化度が低下し、線膨張曲線の屈曲度が大きくなる。また、６０モル％超では、屈曲度は小さくなるが、焼成時にガラス粉体が所望の流動性が得られなくなる。そのため、含有量は合量で、４６〜５９モル％がより好ましく、５０〜５７モル％がさらに好ましい。 The total amount of MgO + ZnO + La 2 O 3 is preferably 45 to 60 mol%. It affects the flowability of the glass powder during firing, the crystallinity of the fired body, and the degree of bending of the linear expansion curve of the fired body. Among these, compared to other glass components, it is a component that particularly affects the degree of bending, and in the present invention, it has been found that there is a correlation as shown in FIG. That is, if it is less than 45 mol%, the degree of crystallinity decreases and the degree of bending of the linear expansion curve increases. On the other hand, if it exceeds 60 mol%, the degree of bending becomes small, but the glass powder cannot obtain the desired fluidity during firing. Therefore, content is a total amount, 46 to 59 mol% is more preferable, 50 to 57 mol% is further more preferable.
本発明のガラス組成物において、アルカリ金属は実質的に含有しない。本明細書において、実質的にアルカリ金属を含有しないとは、不可避的な不純物以外には含有しないとの意味である。 The glass composition of the present invention contains substantially no alkali metal. In the present specification, the phrase “substantially not containing an alkali metal” means that it contains no impurities other than unavoidable impurities.
上記金属酸化物の他に、Ｙ２Ｏ３を含有することが好ましい。一方、Ｙ２Ｏ３は、結晶化度を抑制する特性があるため、焼成時の結晶化する速さを低下させたい場合に用いることが好ましい。そのとき、Ｙ２Ｏ３の含有量は、３〜５質量％が好ましい。 In addition to the metal oxide, Y 2 O 3 is preferably contained. On the other hand, since Y 2 O 3 has a property of suppressing the degree of crystallinity, it is preferably used when it is desired to reduce the crystallization speed during firing. At that time, the content of Y 2 O 3 is preferably 3 to 5% by mass.
次に、本発明のガラス組成物から作製される本発明の封着材について説明する。 Next, the sealing material of this invention produced from the glass composition of this invention is demonstrated.
本発明の封着材は、焼成体として、金属やセラミックス等の被封着材の封着に用いることができる。封着の形態としては、例えば、金属と金属、金属とセラミックスまたはセラミックスとセラミックスがある。特に、焼成した後の焼成体の線膨張係数と同程度線膨張係数を有する被封着材の封着に用いることが好ましい。 The sealing material of this invention can be used for sealing of sealing materials, such as a metal and ceramics, as a sintered body. Examples of the sealing form include metal and metal, metal and ceramic, or ceramic and ceramic. In particular, it is preferably used for sealing a sealing material having a linear expansion coefficient comparable to that of the fired body after firing.
前記封着材としては、本発明のガラス組成物から作製されるガラス粉体からなるガラスフリットまたは、前記ガラスフリット作製されるガラスペースト、プレスフリット若しくはグリーンシートが挙げられる。前記ガラスフリットは、ガラス組成物を粉砕して得られたガラス粉体から、粒径が、３００μｍ以上のものを取り除いて作製される。そして、封着材は必要に応じて、使い分けられる。 Examples of the sealing material include glass frit made of glass powder produced from the glass composition of the present invention, or glass paste, press frit, or green sheet produced from the glass frit. The glass frit is produced by removing particles having a particle size of 300 μm or more from glass powder obtained by pulverizing a glass composition. And a sealing material is properly used as needed.
また、封着材においては、本発明の機能を損なわない範囲で、流動性または線膨張係数を調整する目的で、融点または軟化点が１０００℃以上の耐火物フィラーを添加してもよい。この耐火物フィラーとしては、アルミナ、イットリア等で部分安定化された正方晶ジルコニア、マグネシア、フォルステライト、エンスタタイトおよびディオプサイト等が挙げられる。そして、その添加量は、ガラス粉体とフィラーとの合計体積中、ガラス粉体を８０〜９９体積％、フィラーを１〜２０体積％とすることが好ましい。フィラーの添加量が１体積％未満では、効果が十分に発揮されず、２０体積％を超えると、焼成においてガラス粉体の流動性を阻害するため好ましくない。 In the sealing material, a refractory filler having a melting point or a softening point of 1000 ° C. or more may be added for the purpose of adjusting the fluidity or the linear expansion coefficient within a range not impairing the function of the present invention. Examples of the refractory filler include tetragonal zirconia, magnesia, forsterite, enstatite, and diopsite partially stabilized with alumina, yttria and the like. And it is preferable that the addition amount shall be 80-99 volume% of glass powder and 1-20 volume% of filler in the total volume of glass powder and a filler. If the added amount of the filler is less than 1% by volume, the effect is not sufficiently exhibited, and if it exceeds 20% by volume, the fluidity of the glass powder is impaired during firing, which is not preferable.
本発明のガラスペーストは、前記ガラスフリットと有機ビヒクル等とを混合してペースト化して作製される。ガラスペーストに用いる前記有機ビヒクルとしては、エチルセルロース等のバインダをα‐テルピネオール等の有機溶剤に溶解したものが好ましい。 The glass paste of the present invention is produced by mixing the glass frit and an organic vehicle to form a paste. The organic vehicle used for the glass paste is preferably one in which a binder such as ethyl cellulose is dissolved in an organic solvent such as α-terpineol.
本発明のプレスフリットは、前記ガラスフリットを金型に所望とする量を入れ、５〜５０×１０４ｋＰａの圧力でプレス成形し、１０〜１２０分焼成して焼成して作製される。そして、焼成する温度は、成形形状がガラスの軟化等により変形しないように、ＤＴＡで示される第３屈曲点および第４屈曲点の間の温度で焼成することにより、プレスフリットに変形を生じることなく焼成できる。 The press frit of the present invention is produced by putting a desired amount of the glass frit into a mold, press-molding at a pressure of 5 to 50 × 10 4 kPa, firing and firing for 10 to 120 minutes. The firing temperature is such that the press frit is deformed by firing at a temperature between the third bending point and the fourth bending point indicated by DTA so that the molded shape does not deform due to softening of the glass or the like. Can be fired without any problems.
本発明のグリーンシートは、前記ガラスフリットと有機ビヒクル等とを混合してスラリーとし、ドクターブレード等を用いて透明樹脂フィルム上に塗布し、乾燥して作製される。グリーンシートの作製に用いる前記有機ビヒクルとしては、ブチラール樹脂等のバインダをトルエン等の有機溶剤に溶解したものが好ましい。また、前記透明樹脂フィルムとしては、ＰＥＴフィルム等の離型性のあるシートが好ましい。 The green sheet of the present invention is produced by mixing the glass frit and an organic vehicle into a slurry, applying the slurry onto a transparent resin film using a doctor blade or the like, and drying. As said organic vehicle used for preparation of a green sheet, what melt | dissolved binders, such as butyral resin, in organic solvents, such as toluene, is preferable. The transparent resin film is preferably a sheet having releasability such as a PET film.
本発明の封着材は、ＳＯＦＣ用のシール材として好適である。封着を構成するセラミックス部材および金属部材の表面などに封着材を塗布し、焼成して、所望の構成部材をシールする。そして、ＳＯＦＣのシール材として使用する際には、焼成体の線膨張係数は、被封着材の線膨張係数と同じか、または若干低いことが好ましい。ＳＯＦＣの被封着材としては、例えば、電解質として用いられるＹ２Ｏ３で安定化した立方晶ジルコニア（ＹＳＺ、α＝１００×１０−７／℃）、燃料マニホールドに用いられるＳＵＳ４３０（α＝１２０×１０−７／℃）、熱伝導性と絶縁性にも優れ、電解質の支持体や絶縁層に好適なＭｇＯ（α＝１３０×１０−７／℃）および低温作動型の電解質として期待されるガドリニウム等が添加されたセリア（α＝約１２０×１０−７／℃）等が挙げられる。 The sealing material of the present invention is suitable as a sealing material for SOFC. A sealing material is applied to the surface of the ceramic member and metal member constituting the seal, and fired to seal a desired component. And when using as a sealing material of SOFC, it is preferable that the linear expansion coefficient of a sintered body is the same as that of a sealing material, or a little low. As an SOFC sealing material, for example, cubic zirconia stabilized with Y 2 O 3 used as an electrolyte (YSZ, α = 100 × 10 −7 / ° C.), SUS430 used for a fuel manifold (α = 120) × 10 −7 / ° C.), excellent in thermal conductivity and insulation, expected as MgO (α = 130 × 10 −7 / ° C.) and a low-temperature operating electrolyte suitable for an electrolyte support and insulating layer And ceria (α = about 120 × 10 −7 / ° C.) to which gadolinium or the like is added.
本発明の封着材である、ガラスフリット、ガラスペースト、プレスフリットおよびグリーンシートは、ＣａＯの含有量が低く調整されており、ガラス粉体の焼成時の流動性が良好で、焼成体の屈曲度が小さいため、封着する際に、被封着材との界面内部におけるクラックの発生を抑制できる。そのため、封着部で割れが起こりにくく、絶縁性や気密性の耐久性に優れる。 The glass frit, glass paste, press frit, and green sheet, which are the sealing materials of the present invention, are adjusted to have a low CaO content, have good flowability when the glass powder is fired, and bend the fired body. Since the degree is small, the occurrence of cracks inside the interface with the sealing material can be suppressed when sealing. Therefore, cracking hardly occurs at the sealing portion, and the durability of insulation and airtightness is excellent.
本発明の具体的な態様を以下に説明するが、本発明はこれらに限定されない。ここで、表１〜６中の例３、４、６〜１１が実施例であり、例１、２、５が参考例であり、例１２〜１７が比較例である。表１〜３は、ガラス組成を質量％で、表４〜６はガラス組成をモル％でそれぞれ表示している。 Specific embodiments of the present invention will be described below, but the present invention is not limited thereto. Here, Examples 3, 4 , and 6 to 11 in Tables 1 to 6 are examples, Examples 1 , 2 , and 5 are reference examples, and Examples 12 to 17 are comparative examples. Tables 1 to 3 show the glass composition in mass%, and Tables 4 to 6 show the glass composition in mol%, respectively.
例１〜１７の組成となるようにガラス原料を調合して、混合し、１４５０〜１５００℃の電気炉中で白金ルツボを用いて１．５時間溶融し、２双ローラーを用いて薄板状ガラスに成形および冷却し、ガラス組成物を得た。これを、ボールミル（ニッカトー社製、商品名：ＨＤ−Ｂ−１０５）で平均粒径が１０〜１５μｍ、最大粒径が１５０μｍ以下になるまで粉砕し、その後１００メッシュ（目開き１５０μｍ）の篩にて粗粒を除去してガラス粉体を作製した。 Glass raw materials were prepared and mixed so as to have the composition of Examples 1 to 17, and melted for 1.5 hours using a platinum crucible in an electric furnace at 1450 to 1500 ° C., and a thin glass sheet using two twin rollers. Then, it was molded and cooled to obtain a glass composition. This was pulverized with a ball mill (trade name: HD-B-105, manufactured by Nikkato Co., Ltd.) until the average particle size was 10 to 15 μm and the maximum particle size was 150 μm or less, and then passed through a sieve of 100 mesh (aperture 150 μm). Thus, coarse particles were removed to prepare glass powder.
得られたガラス粉体について、流動性を以下の方法で調べた。その結果を表１に示す。 About the obtained glass powder, fluidity | liquidity was investigated with the following method. The results are shown in Table 1.
（流動性）
φ１５ｍｍの圧粉金型に１．５ｇガラスフリットを充填し、１．４７ｋＮ加重のハンドプレスにて圧粉成型サンプルを作製した。このサンプルをＳＵＳ４３０上で焼成し、流動性を評価した。圧粉体の円柱形状を保持せず流動したものを「○」、円柱形状で角が残っているものを「×」とした。
(Liquidity)
A powder mold of φ15 mm was filled with 1.5 g glass frit, and a compacted sample was prepared by a hand press with a weight of 1.47 kN. This sample was fired on SUS430 and evaluated for fluidity. A green compact that did not retain its cylindrical shape was marked with “◯”, and a cylindrical shape with left corners was marked with “X”.
上述の方法で作製したガラス粉体を、室温から８００℃または８５０℃まで２００℃／時間で昇温し、８００℃または８５０℃に１時間キープした後、室温まで６００℃／時間で冷却し各ガラス粉体の焼成体を得た。 The glass powder produced by the above-mentioned method was heated from room temperature to 800 ° C. or 850 ° C. at 200 ° C./hour, kept at 800 ° C. or 850 ° C. for 1 hour, then cooled to room temperature at 600 ° C./hour, A fired body of glass powder was obtained.
得られた焼成体について、屈伏温度、線膨張係数、線膨張曲線およびこれから算出される屈曲度を調べた。また、ＳＵＳ４３０基板上でガラス粉体を焼成し、焼成後の基板の腐食性と接着界面のクラックの発生を調べた。表１に屈伏温度、平均線膨張係数（α）、屈曲度および金属腐食性を示す。クラックの発生の結果を表３に示す。 The obtained sintered body was examined for yield temperature, linear expansion coefficient, linear expansion curve, and bending degree calculated therefrom. Further, the glass powder was fired on the SUS430 substrate, and the corrosivity of the fired substrate and the occurrence of cracks at the adhesive interface were examined. Table 1 shows the yield temperature, the average linear expansion coefficient (α), the degree of bending, and the metal corrosivity. Table 3 shows the results of the occurrence of cracks.
（屈伏温度）
上記の温度プロファイル作製した焼成体の屈伏温度（単位：℃）を、示差熱分析装置を用いて測定した。
作製した焼成体をφ５ｍｍ×２０ｍｍの円柱状に研磨したサンプルを用い、熱機械分析計（ＲＩＧＡＫＵ社製、商品名：Ｔｈｅｒｍｏｐｌｕｓ２システムＴＭＡ８３１０）で測定した。加重１０ｇ、１０℃／分の条件で室温から９００℃または１０００℃まで加熱し、収縮量５μｍ以上となる温度を屈伏温度とした。
(Bending temperature)
The yield temperature (unit: ° C.) of the fired body produced with the above temperature profile was measured using a differential thermal analyzer.
A sample obtained by polishing the produced fired body into a cylindrical shape of φ5 mm × 20 mm was measured with a thermomechanical analyzer (trade name:
（線膨張係数）
屈伏温度と同様、φ５ｍｍ×２０ｍｍの円柱状に研磨したサンプルを用い、熱機械分析計（ＲＩＧＡＫＵ社製、商品名：Ｔｈｅｒｍｏｐｌｕｓ２システムＴＭＡ８３１０）で測定した。加重１０ｇで、室温から１０℃／分の条件で９００℃または１０００℃まで昇温したときに得られる線膨張曲線から、５０〜８００℃の線膨張係数を求め、そこから５０〜８００℃の線膨張係数の平均値を算出した。
(Linear expansion coefficient)
Similar to the yield temperature, a sample polished in a cylindrical shape of φ5 mm × 20 mm was used and measured with a thermomechanical analyzer (trade name:
（屈曲度）
線膨張係数測定結果から、５０℃を基準とした線膨張係数を３００〜１０００℃において１００℃ごとに算出した。そして、隣り合う１００℃間の線膨張係数の差分の最大値を屈曲度とした。
(Bending degree)
From the linear expansion coefficient measurement results, the linear expansion coefficient based on 50 ° C. was calculated every 300 ° C. at 300 to 1000 ° C. And the maximum value of the difference of the linear expansion coefficient between adjacent 100 degreeC was made into the bending degree.
（腐食性）
流動性評価で得られた焼成体のＳＵＳ４３０とガラスサンプルの端面の外観を目視にて観察した。ＳＵＳ４３０上において、焼成前には見られなかった変質層が見られないものを「○」、見られるものを「×」とした。なお、未測定のものは「−」としている。
(Corrosive)
The appearance of the end faces of the SUS430 and the glass sample of the fired body obtained by the fluidity evaluation was visually observed. On SUS430, the case where the deteriorated layer that was not seen before firing was not seen was “◯”, and the case where it was seen was “x”. In addition, the thing which is not measured is set to "-".
（クラックの発生）
流動性評価で得られた焼成体のＳＵＳ４３０とガラスサンプルを、剥離させ、ＳＵＳ４３０と焼成体の接着面の外観を目視にて観察した。その結果を、表７に示す。
(Occurrence of cracks)
The SUS430 and the glass sample of the fired body obtained by the fluidity evaluation were peeled, and the appearance of the adhesion surface of the SUS430 and the fired body was visually observed. The results are shown in Table 7.
本発明のガラス組成物を主成分とする封着材は、被封着材と接触させて、９００℃未満で焼成し、封着できる。本発明のガラス組成物のガラス粉体を焼成した焼成体は、６００〜１０００度において変形せず、高温にさらされる部分の封着に好適である。特にＳＯＦＣのシール部に好適な封着材として利用できる。 The sealing material containing the glass composition of the present invention as a main component can be brought into contact with the sealing material, fired at less than 900 ° C., and sealed. The fired body obtained by firing the glass powder of the glass composition of the present invention does not deform at 600 to 1000 degrees and is suitable for sealing a portion exposed to a high temperature. In particular, it can be used as a sealing material suitable for a SOFC seal.
Claims (10)
ＳｉＯ２ ２〜３０質量％、
Ｂ２Ｏ３ １０〜３０質量％、
ＭｇＯ ５〜３５質量％、
Ａｌ２Ｏ３ ０を超え１０質量％以下、
ＺｎＯ ０〜２５質量％、
ＢａＯ ０〜３０質量％、
Ｌａ２Ｏ３ ６〜４５質量％、
ＭＯ２ ０〜６質量％（ＭはＣｅ、Ｓｎ、ＺｒおよびＴｉからなる群から選ばれる１種以上の元素）を含有し、
ＣａＯを実質的に含有しないガラス組成物からなることを特徴とするガラスフリット。 It contains substantially no alkali metal oxide and is expressed in mass% in terms of oxide.
SiO 2 2~30% by weight,
B 2 O 3 10 to 30 wt%,
MgO 5 to 35% by mass,
Exceeding 10% by mass exceeding Al 2 O 3 0,
ZnO 0-25% by mass,
BaO 0-30% by mass,
La 2 O 3 6~45 wt%,
MO 2 0-6 mass% (M is one or more elements selected from the group consisting of Ce, Sn, Zr and Ti),
Glass frit, characterized in that it consists essentially Iga Las composition containing CaO.
ＳｉＯSiO ２2 ２〜３０質量％、 2-30% by mass,
ＢB ２2 ＯO ３3 １０〜３０質量％、 10-30% by mass,
ＭｇＯ ５〜３５質量％、MgO 5 to 35% by mass,
ＡｌAl ２2 ＯO ３3 ０を超え１０質量％以下、 More than 0 and 10% by mass or less,
ＺｎＯ ０〜２５質量％、ZnO 0-25% by mass,
ＢａＯ ０〜３０質量％、BaO 0-30% by mass,
ＬａLa ２2 ＯO ３3 ６〜４５質量％、 6-45% by mass,
ＭＯMO ２2 ０〜６質量％（ＭはＣｅ、Ｓｎ、ＺｒおよびＴｉからなる群から選ばれる１種以上の元素）を含有し、 0 to 6% by mass (M is one or more elements selected from the group consisting of Ce, Sn, Zr and Ti),
ＣａＯを実質的に含有しないガラス組成であることを特徴とする結晶化ガラス。A crystallized glass characterized by having a glass composition substantially free of CaO.
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